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The title compound, C13H13Cl5O4, is a highly substituted tricyclic fused-ring diene formed when a nonachlorohomocubane slowly reacts with anhydrous sodium methoxide in tetrahydrofuran at room temperature. Four chloro substituents on the starting material are replaced by methoxy groups. In addition to this replacement, which was detected by NMR techniques, an unexpected opening of the homocubane cage was discovered by the single-crystal X-ray analysis reported herein.
Supporting information
CCDC reference: 177582
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.003 Å
- R factor = 0.037
- wR factor = 0.092
- Data-to-parameter ratio = 16.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
CELLV_02 Alert B The supplied cell volume s.u. differs from that
calculated from the cell parameter s.u.'s by > 4
Calculated cell volume su = 8.55
Cell volume su given = 15.00
Alert Level C:
PLAT_320 Alert C Check Hybridisation of C6 in main residue ?
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
1 Alert Level C = Please check
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) in SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
cis,
syn,
cis-2,3,4,8,9-Pentachloro-1,5,7,7-tetramethoxy-
tricyclo[4.3.0.0
2,5]nona-3,8-diene
top
Crystal data top
C13H13Cl5O4 | Dx = 1.587 Mg m−3 |
Mr = 410.48 | Melting point: not measured K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.390 (2) Å | Cell parameters from 36 reflections |
b = 14.878 (4) Å | θ = 5.5–17.8° |
c = 15.635 (5) Å | µ = 0.86 mm−1 |
β = 91.91 (2)° | T = 294 K |
V = 1718.1 (15) Å3 | Truncated octahedron, colorless |
Z = 4 | 0.50 × 0.44 × 0.16 mm |
F(000) = 832 | |
Data collection top
Bruker P4 diffractometer | 2609 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 26.0°, θmin = 1.9° |
2θ/ω scans | h = −9→9 |
Absorption correction: integration (Wuensch & Prewitt, 1965) | k = 0→18 |
Tmin = 0.807, Tmax = 0.826 | l = 0→19 |
3371 measured reflections | 3 standard reflections every 97 reflections |
3371 independent reflections | intensity decay: 4.0% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0371P)2 + 0.9092P] where P = (Fo2 + 2Fc2)/3 |
3371 reflections | (Δ/σ)max = 0.001 |
203 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
2σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl9 | 0.58738 (9) | 0.43752 (4) | 0.67020 (5) | 0.05135 (18) | |
Cl1 | 0.45659 (9) | 0.29312 (5) | 0.81678 (4) | 0.05333 (19) | |
Cl3 | 0.18248 (12) | 0.04845 (5) | 0.68486 (5) | 0.0693 (2) | |
Cl4 | 0.67040 (11) | 0.11064 (6) | 0.70474 (5) | 0.0768 (3) | |
Cl5 | 0.65016 (11) | 0.18902 (6) | 0.48691 (6) | 0.0746 (3) | |
O8B | 0.4122 (2) | 0.36244 (11) | 0.50604 (10) | 0.0435 (4) | |
O8A | 0.1609 (2) | 0.42311 (11) | 0.57072 (11) | 0.0463 (4) | |
O2 | 0.0747 (2) | 0.22921 (13) | 0.73194 (12) | 0.0528 (5) | |
O6 | 0.1739 (3) | 0.13977 (12) | 0.49045 (11) | 0.0536 (5) | |
C8 | 0.2977 (3) | 0.35758 (15) | 0.57487 (14) | 0.0361 (5) | |
C9 | 0.4147 (3) | 0.36189 (15) | 0.65725 (14) | 0.0349 (5) | |
C1 | 0.3676 (3) | 0.30176 (16) | 0.71445 (13) | 0.0360 (5) | |
C2 | 0.2252 (3) | 0.23812 (16) | 0.68127 (14) | 0.0376 (5) | |
C7 | 0.1992 (3) | 0.26772 (15) | 0.58574 (14) | 0.0366 (5) | |
H7A | 0.0707 | 0.2726 | 0.5689 | 0.044* | |
C6 | 0.2811 (3) | 0.17807 (16) | 0.55458 (15) | 0.0388 (5) | |
C8A | 0.2182 (4) | 0.51533 (17) | 0.5670 (2) | 0.0590 (7) | |
H8AA | 0.1229 | 0.5511 | 0.5414 | 0.089* | |
H8AB | 0.3240 | 0.5197 | 0.5333 | 0.089* | |
H8AC | 0.2459 | 0.5367 | 0.6239 | 0.089* | |
C5 | 0.4856 (3) | 0.16610 (16) | 0.55752 (17) | 0.0440 (6) | |
C4 | 0.4940 (3) | 0.13632 (16) | 0.63690 (16) | 0.0433 (6) | |
C3 | 0.2959 (3) | 0.14391 (16) | 0.65065 (15) | 0.0398 (5) | |
C8B | 0.3220 (4) | 0.3510 (2) | 0.42394 (16) | 0.0601 (8) | |
H8BA | 0.4097 | 0.3521 | 0.3800 | 0.090* | |
H8BB | 0.2365 | 0.3989 | 0.4145 | 0.090* | |
H8BC | 0.2596 | 0.2944 | 0.4225 | 0.090* | |
C6A | 0.2326 (5) | 0.0549 (2) | 0.4593 (2) | 0.0740 (10) | |
H6AA | 0.1507 | 0.0349 | 0.4143 | 0.111* | |
H6AB | 0.2348 | 0.0119 | 0.5051 | 0.111* | |
H6AC | 0.3520 | 0.0609 | 0.4375 | 0.111* | |
C2A | −0.0212 (4) | 0.3109 (2) | 0.7433 (2) | 0.0751 (10) | |
H2AA | −0.1280 | 0.2994 | 0.7748 | 0.113* | |
H2AB | −0.0550 | 0.3358 | 0.6885 | 0.113* | |
H2AC | 0.0548 | 0.3528 | 0.7745 | 0.113* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl9 | 0.0452 (3) | 0.0460 (4) | 0.0621 (4) | −0.0090 (3) | −0.0098 (3) | −0.0045 (3) |
Cl1 | 0.0570 (4) | 0.0721 (5) | 0.0303 (3) | 0.0087 (3) | −0.0071 (3) | −0.0010 (3) |
Cl3 | 0.0817 (5) | 0.0531 (4) | 0.0729 (5) | −0.0183 (4) | 0.0002 (4) | 0.0222 (4) |
Cl4 | 0.0629 (5) | 0.0949 (6) | 0.0705 (5) | 0.0337 (4) | −0.0278 (4) | −0.0189 (4) |
Cl5 | 0.0679 (5) | 0.0767 (5) | 0.0813 (6) | 0.0070 (4) | 0.0342 (4) | 0.0045 (4) |
O8B | 0.0518 (10) | 0.0467 (10) | 0.0321 (9) | −0.0085 (8) | 0.0028 (7) | 0.0024 (7) |
O8A | 0.0426 (9) | 0.0397 (9) | 0.0560 (11) | 0.0042 (7) | −0.0085 (8) | 0.0072 (8) |
O2 | 0.0384 (10) | 0.0650 (12) | 0.0559 (11) | 0.0012 (8) | 0.0140 (8) | 0.0152 (9) |
O6 | 0.0651 (12) | 0.0441 (10) | 0.0501 (11) | −0.0027 (9) | −0.0214 (9) | −0.0043 (8) |
C8 | 0.0362 (12) | 0.0383 (12) | 0.0333 (12) | 0.0011 (10) | −0.0041 (9) | 0.0020 (10) |
C9 | 0.0311 (11) | 0.0372 (12) | 0.0362 (12) | 0.0015 (9) | −0.0028 (9) | −0.0062 (10) |
C1 | 0.0338 (11) | 0.0469 (13) | 0.0269 (11) | 0.0064 (10) | −0.0021 (9) | −0.0011 (10) |
C2 | 0.0320 (12) | 0.0453 (13) | 0.0354 (12) | 0.0004 (10) | 0.0008 (9) | 0.0067 (10) |
C7 | 0.0309 (12) | 0.0407 (13) | 0.0377 (12) | −0.0008 (10) | −0.0062 (9) | 0.0053 (10) |
C6 | 0.0417 (13) | 0.0372 (12) | 0.0368 (13) | −0.0049 (10) | −0.0071 (10) | 0.0023 (10) |
C8A | 0.0664 (19) | 0.0394 (15) | 0.0698 (19) | 0.0083 (13) | −0.0174 (15) | 0.0039 (13) |
C5 | 0.0437 (14) | 0.0400 (13) | 0.0487 (15) | 0.0000 (11) | 0.0064 (11) | −0.0044 (11) |
C4 | 0.0438 (14) | 0.0401 (13) | 0.0453 (14) | 0.0072 (11) | −0.0076 (11) | −0.0051 (11) |
C3 | 0.0407 (13) | 0.0392 (13) | 0.0391 (13) | −0.0036 (10) | −0.0048 (10) | 0.0101 (10) |
C8B | 0.088 (2) | 0.0576 (17) | 0.0345 (14) | −0.0144 (16) | −0.0066 (14) | 0.0051 (12) |
C6A | 0.097 (3) | 0.0507 (18) | 0.073 (2) | −0.0043 (17) | −0.0237 (19) | −0.0157 (16) |
C2A | 0.0550 (18) | 0.085 (2) | 0.087 (2) | 0.0233 (17) | 0.0288 (17) | 0.0143 (19) |
Geometric parameters (Å, º) top
Cl9—C9 | 1.708 (2) | C7—C6 | 1.550 (3) |
Cl1—C1 | 1.714 (2) | C7—H7A | 0.9800 |
Cl3—C3 | 1.742 (2) | C6—C5 | 1.520 (3) |
Cl4—C4 | 1.696 (2) | C6—C3 | 1.586 (3) |
Cl5—C5 | 1.704 (3) | C8A—H8AA | 0.960 |
O8B—C8 | 1.393 (3) | C8A—H8AB | 0.960 |
O8B—C8B | 1.436 (3) | C8A—H8AC | 0.960 |
O8A—C8 | 1.405 (3) | C5—C4 | 1.317 (4) |
O8A—C8A | 1.438 (3) | C4—C3 | 1.491 (3) |
O2—C2 | 1.393 (3) | C8B—H8BA | 0.960 |
O2—C2A | 1.421 (3) | C8B—H8BB | 0.960 |
O6—C6 | 1.380 (3) | C8B—H8BC | 0.960 |
O6—C6A | 1.426 (3) | C6A—H6AA | 0.960 |
C8—C9 | 1.529 (3) | C6A—H6AB | 0.960 |
C8—C7 | 1.534 (3) | C6A—H6AC | 0.960 |
C9—C1 | 1.320 (3) | C2A—H2AA | 0.960 |
C1—C2 | 1.495 (3) | C2A—H2AB | 0.960 |
C2—C7 | 1.563 (3) | C2A—H2AC | 0.960 |
C2—C3 | 1.576 (3) | | |
| | | |
C8—O8B—C8B | 114.15 (19) | O8A—C8A—H8AB | 109.5 |
C8—O8A—C8A | 116.85 (19) | H8AA—C8A—H8AB | 109.5 |
C2—O2—C2A | 113.6 (2) | O8A—C8A—H8AC | 109.5 |
C6—O6—C6A | 116.1 (2) | H8AA—C8A—H8AC | 109.5 |
O8B—C8—O8A | 112.52 (18) | H8AB—C8A—H8AC | 109.5 |
O8B—C8—C9 | 107.93 (18) | C4—C5—C6 | 94.8 (2) |
O8A—C8—C9 | 113.33 (18) | C4—C5—Cl5 | 131.7 (2) |
O8B—C8—C7 | 115.68 (19) | C6—C5—Cl5 | 133.38 (19) |
O8A—C8—C7 | 105.45 (18) | C5—C4—C3 | 95.4 (2) |
C9—C8—C7 | 101.56 (17) | C5—C4—Cl4 | 132.5 (2) |
C1—C9—C8 | 112.8 (2) | C3—C4—Cl4 | 131.65 (19) |
C1—C9—Cl9 | 125.39 (18) | C4—C3—C2 | 116.6 (2) |
C8—C9—Cl9 | 121.79 (17) | C4—C3—C6 | 85.69 (18) |
C9—C1—C2 | 113.12 (19) | C2—C3—C6 | 89.41 (17) |
C9—C1—Cl1 | 125.55 (19) | C4—C3—Cl3 | 117.86 (18) |
C2—C1—Cl1 | 121.33 (17) | C2—C3—Cl3 | 117.64 (17) |
O2—C2—C1 | 115.4 (2) | C6—C3—Cl3 | 122.22 (17) |
O2—C2—C7 | 119.68 (19) | O8B—C8B—H8BA | 109.5 |
C1—C2—C7 | 102.46 (18) | O8B—C8B—H8BB | 109.5 |
O2—C2—C3 | 111.55 (19) | H8BA—C8B—H8BB | 109.5 |
C1—C2—C3 | 115.60 (18) | O8B—C8B—H8BC | 109.5 |
C7—C2—C3 | 89.53 (17) | H8BA—C8B—H8BC | 109.5 |
C8—C7—C6 | 121.56 (19) | H8BB—C8B—H8BC | 109.5 |
C8—C7—C2 | 107.92 (18) | O6—C6A—H6AA | 109.5 |
C6—C7—C2 | 91.20 (17) | O6—C6A—H6AB | 109.5 |
C8—C7—H7A | 111.4 | H6AA—C6A—H6AB | 109.5 |
C6—C7—H7A | 111.4 | O6—C6A—H6AC | 109.5 |
C2—C7—H7A | 111.4 | H6AA—C6A—H6AC | 109.5 |
O6—C6—C5 | 121.3 (2) | H6AB—C6A—H6AC | 109.5 |
O6—C6—C7 | 111.29 (19) | O2—C2A—H2AA | 109.5 |
C5—C6—C7 | 119.29 (19) | O2—C2A—H2AB | 109.5 |
O6—C6—C3 | 125.1 (2) | H2AA—C2A—H2AB | 109.5 |
C5—C6—C3 | 84.07 (17) | O2—C2A—H2AC | 109.5 |
C7—C6—C3 | 89.62 (17) | H2AA—C2A—H2AC | 109.5 |
O8A—C8A—H8AA | 109.5 | H2AB—C2A—H2AC | 109.5 |
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